Poly(aryl ether sulfones) have been known for about two decades; they are tough linear polymers that possess a number of attractive features such as excellent high temperature resistance, good electrical properties, and very good hydrolytic stability. Two poly(aryl ether sulfones) are commercially available. A poly(aryl ether sulfone) is available from Imperial Chemical Industries Limited. It has the formula (1) ##STR1## and is produced by polycondensation of 4,4'-dihydroxydiphenyl sulfone with 4,4'-dichlorophenyl sulfone, as described in Canadian Pat. No. 847,963. The polymer contains no aliphatic moieties and has a heat deflection temperature of approximately 210.degree. C. Another commercial poly(aryl ether) is available from Amoco Performance Products, Inc. under the trademark UDEL.RTM.. It corresponds to formula (2) and has a heat deflection temperature of about 180.degree. C. ##STR2##
Polymer (2) is prepared via the nucleophilic polycondensation reaction of 2,2-bis(4-hydroxyphenyl) propane ("bisphenol-A") with 4,4,-dichlorodiphenyl sulfone. This method, described by Johnson et al., Journal of Polymer Science, A-1, Vol. 5, 1967, pp. 2415-2427, and Johnson et al., U.S. Pat. Nos. 4,107,837 and 4,175,175, has been shown to be quite general and applicable for the synthesis of a broad range of other poly(aryl ethers) (hereinafter called PAE's ). Using this approach, a host of PAE's having wide ranging properties was prepared.
Materials (1) and (2) display relatively low glass-transitions and, hence, low heat distortion temperatures. The drawback is serious, since it makes the two polymers unsuitable in applications where a very high Tg is important. Such applications include, for example, the area of composites which often require a matrix capable of maintaining structural integrity at (very) high temperatures. Thus, an intensive search for high Tg poly(aryl ethers) has been underway for years.
An example of high Tg poly(aryl ethers) that were studied are those containing the 4,4'-bis(phenylsulfonyl)biphenyl units (3): ##STR3## U.S. Pat. No. 3,647,751 depicts polymers of formula (4): ##STR4## wherein Ar is defined as a diphenylene or naphthylene radical or a polynuclear divalent radical of the formula: ##STR5## where Z is a divalent aliphatic, cycloaliphatic or arylaliphatic radical containing 1 to 8 carbon atoms or --O--, --S--, --SO--, --SO.sub.2 --, or --CO--.
U.S. Pat. No. 3,634,355 describes a number of polymers prepared from 4,4'-bis(4-chlorophenylsulphonyl)biphenyl (5). ##STR6##
For instance, in Example 15 of the above patent, the following polymer is provided: ##STR7##
Example 16 depicts the polymer containing units (6) and (7) in a 4:1 molar ratio. ##STR8##
Example 17 shows the same structure, except that units (6) and (7) are present in a 1:1 ratio.
The homopolymer (7) is described in U.S. Pat. No. 4,009,149.
Copolymers containing units (3) are also the subject of a patent application (Ser. No. 81,344), filed on Aug. 4, 1987 in the names of James Elmer Harris, Louis Michael Maresca and Markus Matzner, titled "Polyaryl Ether Sulfones", and commonly assigned.
Other poly(aryl ethers) displaying high glass transition temperatures are, for example, those containing terphenylene, naphthylene, anthracenylene and fluorene-9,9-bis(phenylene) units (8): ##STR9##
All of the above materials often show two basic drawbacks: either the required monomers are difficult to come by and must be prepared via long and tedious synthetic routes; and/or it is very difficult to prepare the final high Tg polymers at satisfactory molecular weights.